[0001] Our invention provides graft copolymers containing polydiorganosiloxane and polybutylene
grafts. More particularly our invention teaches a graft copolymer having a backbone
and two or more polymeric side chains, the copolymer formed from the copolymerization
of at least one acryloxyalkyl - functional polydiorganosiloxane macromonomer, at least
one acryl-terminated, carboxylfunctional polybutylene macromonomer, and at least one
ethylenically unsaturated monomer which is copolymerizable with the polydiorganosiloxane
and polybutylene macromonomers. Our invention also provides a method of making graft
copolymers containing polydiorganosiloxane and polybutylene grafts.
[0002] Graft copolymers containing polyorganosiloxane grafts have been described in the
art. For example, U.S. Patent 5,241,035 discloses a graft copolymer comprising a trunk
polymer having a vinyl chloride/vinyl alcohol copolymer containing vinyl chloride
and vinyl alcohol as the essential constituent monomer units and a branch polymer
comprising an polyorganosiloxane grafted onto said trunk polymer.
[0003] WO 96/00562 discloses a hair care composition comprising (A) a thermoplastic elastomeric
copolymer having a backbone and two or more hydrophobic polymeric side chains, said
copolymer formed from the copolymerization of randomly repeating A, B and C units
wherein the copolymer comprises (i) from 20 to 90% by weight of the A units, wherein
the A units are monomer units copolymerizable with the B and C units, (ii) from 10
to 60% by weight of the B unit, wherein the B units are hydrophobic macromonomer units
having a polymeric portion and a moiety copolymerizable with the A and C units, and
(iii) from 0 to 20% by weight of the C units, wherein the C units are polysiloxane
macromonomer units having a polymeric portion and a moiety copolymerizable with the
A and B units, wherein the A units, in conjunction with the copolymerizable moieties
of the B units and the C units, form the backbone, wherein the polymeric portion of
the B units forms the hydrophobic side chains, wherein the copolymer has a weight
average molecular weight greater than 10,000, and wherein the copolymer exhibits at
least two distinct Tg values, the first Tg corresponding to the backbone and having
a value less than 0°C., and the second Tg corresponding to the hydrophobic polymeric
side chains and having a value greater than 25°C.; and (B) a water-insoluble, volatile
solvent for the copolymer suitable for application to the hair.
[0004] U.S. Patent 5,665,828 discloses a polybutylene polymer or oligomer which contains
at least one acryl group, the polybutylene being prepared by reacting an anhydride-functional
polybutylene or derivative thereof, with an acryl-functional compound having at least
one hydroxyl-containing group, chlorine, isocyanate group, epoxy group or amine group
in its molecule.
[0005] U.S. Patent 5,371,379 discloses a method of making a copolymer in an emulsion comprising
heating and shearing a reaction mixture formed by combining (i) water, (ii) an anionic
surfactant, a cationic surfactant, a nonionic surfactant or a combination thereof,
optionally (iii) a co-surfactant which is a hydrophobic solvent or a compound selected
from fatty alcohols, n-alkanes and halogen substituted n-alkanes, (iv) a monoacryloxyalkyl
terminated polydiorganosiloxane macromonomer or a monomethacryloxy-terminated polydiorganosiloxane
macromonomer, (v) an acrylic or methacrylic- functional polyisobutylene macromonomer,
optionally (vi) a radical polymerizable monomer and (vii) a free radical initiator.
[0006] Our invention provides organopolysiloxane-modified graft copolymers having two or
more polymeric side chains, the copolymer formed from the copolymerization of at least
one acryloxyalkyl-functional polydiorganosiloxane macromonomer, at least one acryl-terminated,
carboxyl-functional polybutylene macromonomer, and at least one ethylenically unsaturated
monomer which is copolymerizable with the polydiorganosiloxane and polybutylene macromonomers.
[0007] Our invention also teaches a method of making graft copolymers containing polydiorganosiloxane
and polybutylene grafts comprising (I) heating a mixture comprising at least one ethylenically
unsaturated monomer, at least one acryloxyalkyl-functional polydiorganosiloxane macromonomer,
at least one acryl-terminated, carboxyl-functional polybutylene macromonomer and a
free radical initiator. The mixture can further comprise a solvent or the mixture
can also comprise at least one surfactant and water or the mixture can further comprise
at least one suspending agent and water.
[0008] When the ethylenically unsaturated monomer is a vinyl ester such as vinyl acetate,
the method can further comprise adding a base compound to the product of (I).
[0009] An object of our invention is to make a graft copolymer using radically copolymerizable
macromonomeric polydiorganosiloxanes and macromonomeric polybutylenes.
[0010] Another object of our invention is to produce graft copolymers which have good water
repellency and good water impermeability in addition to good film forming properties.
[0011] Our invention provides a graft copolymer comprising a backbone and at least two polymeric
side chains, the graft copolymer formed from the copolymerization of randomly repeating
ethylenically unsaturated monomer units, acryloxyalkyl-functional polydiorganosiloxane
macromonomer units, and acryl-terminated, carboxyl-functional polybutylene macromonomer
units, wherein the copolymer comprises: (A) at least one ethylenically unsaturated
monomer, (B) at least one acryl-terminated, carboxyl-functional polybutylene macromonomer
having its formula selected from
(i)
(ii)
(iii) a mixture of (i) and (ii),
(iv)
(v)
(vi) a mixture of (iv) and (v),
(vii)
(viii)
(ix)
(x) a mixture of (viii) and (ix),
(xi)
(xii)
(xiii) a mixture of (xi) and (xii),
(xiv)
(xv)
(xvi) a mixture of (xiv) and (xv),
(xvii)
(xviii)
or
(xix) a mixture of (xvii) and (xviii), wherein Z represents a polybutylene chain,
G is independently an alkylene group having 2 to 10 carbon atoms, G' is independently
an alkylene group having from 1 to 10 carbon atoms, L is independently selected from
hydrogen or an alkyl group having from 1 to 18 carbon atoms, R2 is selected from methyl, ethyl or propyl and R1 is independently an alkyl radical having from 1 to 6 carbon atoms, and (C) at least
one acryloxyalkyl-functional polydiorganosiloxane macromonomer, wherein the ethylenically
unsaturated monomer units, in conjunction with the copolymerizable moieties of the
acryloxyalkyl-functional polydiorganosiloxane macromonomer units and the acryl-terminated,
carboxyl-functional polybutylene macromonomer units, form the backbone, and wherein
the polymeric portion of the acryloxyalkyl-functional polydiorganosiloxane macromonomer
units form at least one side chain and the polymeric portion of the acryl-terminated,
carboxyl-functional polybutylene macromonomer units form at least one side chain.
[0012] "Graft copolymer" is a term familiar to those of ordinary skill in polymer science
and is used to describe copolymers onto which another chemical moiety has been added
or "grafted" and means that these copolymers can contain pendant polymeric side chains,
or in other words, these polymers can be formed from the "grafting" or incorporation
of polymeric side chains onto or into the copolymer.
[0013] The term "macromonomer" is one familiar to those of ordinary skill in polymer science
and is used to describe a polymeric material containing a polymerizable moiety. In
other words, a macromonomer is a macromolecular monomer, which is essentially a high
molecular weight type of monomer building block unit which can be used in a polymerization
reaction to form polymers with itself, with other monomers or with other macromonomers.
[0014] The term "carboxyl-functional" is used herein to mean materials that contain at least
one protonated or deprotonated carboxylic acid group or a derivative thereof, for
example an ester group, an anhydride group or an amido group.
[0015] The ethylenically unsaturated monomer (A) must be copolymerizable with components
(B) and (C). Either a single ethylenically unsaturated monomer or combinations of
two or more ethylenically unsaturated monomers can be used. The term " copolymerizable"
as used herein means monomers that can be copolymerized using any conventional synthetic
techniques. Monomers that are copolymerizable using conventional free radical initiated
techniques are preferred. The term " ethylenically unsaturated" is used herein to
mean monomers that contain at least one polymerizable carbon-carbon double bond (which
can be mono-, di-, tri- or tetra-substituted).
[0016] The ethylenically unsaturated monomers of component (A) are exemplified by acrylic
acid esters, vinyl esters, N-alkyl acrylamides, alkyl vinyl ethers, alkyl substituted
styrenes, dienes and acrylonitrile.
[0017] The acrylic acid esters are exemplified by compounds having the formula R
3-O-C(O)-CR
4=CHR
5 wherein R
3 is selected from alkyl groups having from 1 to 30 carbon atoms, arylalkyl groups
having from 1 to 30 carbon atoms, alkoxyalkyl groups having from 1 to 30 carbon atoms
or hydroxyalkyl groups having from 1 to 30 carbon atoms, R
4 and R
5 are independently selected from hydrogen, an alkyl group having from 1 to 8 carbon
atoms, an alkoxy group having from 1 to 8 carbon atoms, an alkoxyalkyl group having
from 1 to 8 carbon atoms or a hydroxyalkoxy group having from 1 to 8 carbon atoms.
The alkyl groups, arylalkyl groups, alkoxy groups and hydroxyalkyl groups of R
3 can be straight chain, branched chain or cyclic and may be substituted with one or
more halogen atoms such as fluorine or chlorine.
[0018] The alkyl groups of R
3 are exemplified by methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl,
hexadecyl, octadecyl, isobornyl, - C
20H
41, -C
22H
45, -C
24H
49, -C
26H
53, -C
28H
57 and -C
30H
61. The arylalkyl groups of R
3 are exemplified by alkyl groups as defined above substituted with one or more aryl
groups exemplified by phenyl. The alkoxyalkyl groups of R
3 are exemplified by alkyl groups as defined above substituted with one or more alkoxy
groups exemplified by methoxy, ethoxy and phenoxy. The hydroxyalkyl groups of R
3 are exemplified by alkyl groups as defined above substituted with one or more hydroxy
(-OH) groups.
[0019] The alkyl groups of R
4 and R
5 are exemplified by methyl, ethyl, propyl, butyl, hexyl and octyl. The alkoxy groups
of R
4 and R
5 are exemplified by methoxy and ethoxy. The alkoxyalkyl groups of R
4 and R
5 are exemplified by 2-methoxyethyl and 2-ethoxyethyl. The hydroxyalkoxy groups of
R
4 and R
5 are exemplified by 2-hydroxyethoxy.
[0020] The acrylic acid esters are exemplified by methyl acrylate, ethyl acrylate, butyl
acrylate, isobutyl acrylate, methylbutyl acrylate, ethylbutyl acrylate, dimethylbutyl
acrylate, propyl acrylate, isopropyl acrylate, pentyl acrylate, hexyl acrylate, heptyl
acrylate, methylpentyl acrylate, octyl acrylate, dimethyloctyl acrylate, 2-ethylhexyl
acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, tetradecyl
acrylate, tridecyl acrylate, hexadecyl acrylate, octadecyl acrylate, 2-phenylethyl
acrylate, 1,1,1-trifluoroethyl acrylate, benzyl acrylate, cyclohexyl acrylate, 1,1-dihydroperfluorohexyl
acrylate, 1,1-dihydroperfluorodecyl acrylate, 1,1-dihydroper-fluoropentyl acrylate,
heptafluorobutyl acrylate, hydroxypropyl acrylate, methoxybutyl acrylate, phenoxyethyl
acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate,
t-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate,
2-ethylhexyl methacrylate, n-decyl methacrylate, tetradecyl methacrylate, 2-ethylhexyl
ethacrylate and mixtures thereof. Preferred acrylic acid esters are selected from
methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate,
ethylbutyl acrylate, nonyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl
acrylate, isobornyl acrylate, hydroxypropyl acrylate and mixtures thereof, with methyl
acrylate being especially preferred.
[0021] The vinyl esters are exemplified by vinyl acetate. The copolymers of this invention
formed by utilizing the vinyl ester can then subsequently hydrolyzed to various degrees
to form a backbone component having varying degrees of polyvinylalcohol.
[0022] The N-alkyl acrylamides are exemplified by N-octyl acrylamide, N-octyl methacrylamide,
N-octyl ethacrylarnide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N-(2-ethylhexyl)
acrylamide, N-hexadecyl acrylamide, N,N-methylpropyl acrylamide, N,N-methylpropyl
methacrylamide and mixtures thereof.
[0023] The alkyl vinyl ethers are exemplified by ethyl vinyl ether, decyl vinyl ether, hexadecyl
vinyl ether, hexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, octyl
vinyl ether, propyl vinyl ether, s-butyl vinyl ether and mixtures thereof.
[0024] The alkyl substituted styrenes are exemplified by 4-nonyl styrene, 4-octyl styrene,
4-(2-ethylhexyl) styrene, 3-octyl styrene, 2-octyl styrene, 4-isobutyl styrene, 3,5-dimethyl
styrene, 2-methyl-4-isopropyl styrene and mixtures thereof.
[0025] It is preferred for purposes of this invention that component (A) is an acrylic acid
ester as described above.
[0026] Preferably, component (A), the ethylenically unsaturated monomer, is present in an
amount of from 10 to 99.8 weight percent (wt%), and more preferably from 20 to 60
wt%, said wt% being based on the total weight of the copolymer.
[0027] The polybutylene chain of (B) can comprise repeat units having the following formulas
as well as rearranged products such as
-(CH
2CH
2CH
2CH
2)- and
[0028] The preferred component (B) is an oligomer or polymer wherein a predominant proportion
of the repeat units are isobutylene units and which has a number average molecular
weight of 200 to 200,000, preferably 200 to 2,000.
[0029] In formulas (i)-(xix), the alkylene groups of G are exemplified by ethylene, -CH
2CH(CH
3)-, propylene, -CH
2CH(CH
3)CH
2-, butylene, pentylene, trimethylene, 2-methyltrimethylene, pentamethylene, hexamethylene,
3-ethyl-hexamethylene, octamethylene and decamethylene. The alkylene groups of G'
are exemplified by methylene, ethylene, -CH
2CH(CH
3)-, propylene, -CH
2CH(CH
3)CH
2-, butylene, pentylene, trimethylene, 2 -methyltrimethylene, pentamethylene, hexamethylene,
3-ethyl-hexamethylene, octamethylene and decamethylene.
[0030] The alkyl groups of L in formulas (i)-(xix) are exemplified by methyl, ethyl, propyl,
butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl. Preferably
L is selected from hydrogen or methyl. The group R
1 is exemplified by methyl, ethyl, propyl, butyl and hexyl.
[0031] Preferably the acryl-terminated, carboxyl-functional polybutylene macromonomer is
selected from
(i)
(ii)
or
(iii) a mixture of (i) and (ii), wherein Z, G and L are defined as described above.
[0032] Preferably, component (B), the acryl-terminated, carboxyl-functional polybutylene
macromonomer, is present in amount from 0.1 to 90 wt%, and more preferably from 5
to 70 wt%, said wt% being based on the total weight of the copolymer.
[0033] Component (C), the acryloxy-functional polydiorganosiloxane macromonomer is exemplified
by acryloxyalkyl-functional organopolysiloxanes having the formula:
wherein R
6 is an alkyl group having from 1 to 18 carbon atoms, R
7 is an alkyl group having from 1 to 10 carbon atoms, a has a value of at least 1,
preferably at least 3, and more preferably at least 10 and Y is a group having the
formula -R
9-O-C(O)-CR
8=CH
2 wherein R
8 is selected from hydrogen or an alkyl group having from 1 to 18 carbon atoms and
R
9 is an alkylene group having from 1 to 10 carbon atoms.
[0034] The alkyl groups of R
6, R
7 and R
8 are as described above including preferred embodiments thereof. The alkylene groups
of R
9 are as described above including preferred embodiments thereof. Preferably, R
6 is methyl, R
7 is selected from methyl, ethyl, propyl, n-butyl, sec-butyl and tert-butyl, R
8 is hydrogen or methyl and R
9 is selected from ethylene, propylene and butylene. Preferably a has a value of from
10 to 300.
[0035] Preferably, component (C), the acryloxy-functional organopolysiloxane macromonomer,
is present in an amount from 0.1 to 90 wt%, and more preferably from 0.1 to 40 wt%,
said wt% being based on the total weight of the copolymer.
[0036] Particularly preferred polymers are exemplified by (the weight percents below refer
to the amount of reactants added in the polymerization reaction, not necessarily the
amount in the finished polymer): 50 wt% methyl acrylate/30 wt% acryl-terminated, carboxyl-functional
polybutylene macromonomer/20 wt% acryloxyalkyl-functional polydimethylsiloxane macromonomer;
10 wt% methyl acrylate/ 70 wt% acryl-terminated, carboxyl-functional polybutylene
macromonomer/20 wt% acryloxyalkyl- functional polydimethylsiloxane macromonomer; 50
wt% methyl acrylate/30 wt% acryl-terminated, carboxyl-functional polybutylene macromonomer/20
wt% acryloxyalkyl-functional polydimethylsiloxane macromonomer; and 10 wt% methyl
acrylate/70 wt% acryl-terminated, carboxyl-functional polybutylene macromonomer/20
wt% acryloxyalkyl- functional polydimethylsiloxane macromonomer.
[0037] The graft copolymers of this invention can be prepared by free radical polymerization
of monomer (A) with macromonomers (B) and (C). It is not intended to necessarily exclude
from this invention any copolymers made by means other than free radical polymerization,
so long as the product has the desired physical properties. The graft copolymers herein
are formed from randomly repeating ethylenically unsaturated monomer units, acryl-terminated,
carboxyl-functional polybutylene units and acryloxyalkyl-functional polydimethylsiloxane
units.
[0038] This invention further relates to a method of making graft copolymers comprising
randomly repeating ethylenically unsaturated monomer units, acryl-terminated, carboxyl-functional
polybutylene units and acryloxyalkyl-functional polydimethylsiloxane units, the method
comprising (I) heating a mixture comprising (A) at least one ethylenically unsaturated
monomer, (B) an acryl-terminated, carboxyl-functional polybutylene macromonomer having
a formula selected from
(i)
(ii)
(iii) a mixture of (i) and (ii),
(iv)
(v)
(vi) a mixture of (iv) and (v),
(vii)
(viii)
(ix)
(x) a mixture of (viii) and (ix),
(xi)
(xii)
(xiii) a mixture of (xi) and (xii),
(xiv)
(xv)
(xvi) a mixture of (xiv) and (xv),
(xvii)
(xviii)
(xix) a mixture of (xvii) and (xviii), wherein Z represents a polybutylene chain,
G is independently an alkylene group having 2 to 10 carbon atoms, G' is independently
an alkylene group having from 1 to 10 carbon atoms, L is independently selected from
hydrogen or an alkyl group having from 1 to 18 carbon atoms, R2 is selected from methyl, ethyl or propyl and R1 is independently an alkyl radical having from 1 to 6 carbon atoms, (C) an acryloxyalkyl-functional
polydiorgano-siloxane macromonomer and (D) an initiator.
[0039] Components (A)-(C) are as described hereinabove including preferred embodiments and
amounts thereof. Component (D) in this invention is an initiator. Preferably component
(D) is a free radical initiator exemplified by peroxide initiators, azo initiators,
redox intitiators and photochemical initiators. The peroxide initiators are exemplified
by diacyl peroxides, peroxyesters, dialkyl peroxides and peroxydicarbonates. Especially
preferred peroxide initiators are exemplified by dibenzoyl peroxide, t-butyl peroctoate,
dicumyl peroxide, diisopropyl peroxydicarbonate and a preferred azo initiator is 2,2-azobisisobutyronitrile.
[0040] Preferably, component (D), the initiator, is present in an amount from 0.05 to 5
wt%, and more preferably from 0.1 to 1 wt%, said wt% being based on the total weight
of the formulation.
[0041] If the copolymers of this invention are produced by solution polymerization then
the mixture can further comprise (E), a solvent, which is exemplified by aliphatic
hydrocarbons such as pentane, hexane, heptane, octane and nonane, aromatic hydrocarbons
such as benzene, toluene and xylene; ketones such as acetone, methylethyl ketone and
methylisobutyl ketone and halogenated diluents such as fluorine-, chlorine- and bromine-,
substituted aliphatic or aromatic hydrocarbons such as trichloro-ethane, perchloroethylene,
bromobenzene and the like. Two or more solvents may be used together. The solvent
is preferably selected from benzene, toluene or xylene.
[0042] The amount of solvent is not critical and may be readily determined by one skilled
in the art. Generally, component (E), the solvent, is present in an amount of 0 to
1000 parts by weight, and preferably from 100 to 300 parts by weight, per 100 parts
by weight of components (A)-(D).
[0043] If the copolymers of this invention are produced by emulsion polymerization then
the mixture can further comprise (E'), at least one surfactant and water, and the
surfactants are exemplified by (i) at least one anionic surfactant, (ii) at least
one nonionic surfactant, (iii) at least one cationic surfactant, a mixture of (i)
and (ii) and a mixture of (ii) and (iii).
[0044] The anionic surfactants may be selected from any anionic surfactant known in the
art as useful in emulsion polymerization. Examples of suitable anionic surfactants
include alkali metal sulforicinates, sulfonated glyceryl esters of fatty acids such
as sulfonated monoglycerides of coconut oil acids, salts of sulfonated monovalent
alcohol esters such as sodium oleylisethionate, amides of amino sulfonic acids such
as the sodium salt of oleyl methyl tauride, sulfonated products of fatty acids nitriles
such as palmitonitrile sulfonate, sulfonated aromatic hydrocarbons such as sodium
alkyl-naphthalene monosulfonate, condensation products of naphthalene sulfonic acids
with formaldehyde, sodium octahydroanthracene sulfonate, alkali metal alkyl sulfates
such as ammonium lauryl sulfate or triethanol amine lauryl sulfate, ether sulfates
having alkyl groups of 8 or more carbon atoms such as sodium lauryl ether sulfate
or sodium alkyl aryl ether sulfates, alkylaryl-sulfonates having 1 or more alkyl groups
of 8 or more carbon atoms, alkylbenzenesulfonic acids which are exemplified by hexylbenzenesulfonic
acid, octylbenzene-sulfonic acid, decylbenzenesulfonic acid, dodecyl-benzenesulfonic
acid, cetylbenzenesulfonic acid and myristylbenzenesulfonic acid, salts of alkylbenzene-sulfonic
acids, alkyltoluenesulfonic acids, alkylxylenesulfonic acids, sulfuric esters of polyoxyethylene
alkyl ether including CH
3 (CH
2)
6CH
2O(C
2H
4O)
2SO
3H, CH
3 (CH
2)
7CH
2O(C
2H
4O)
3.
5SO
3H, CH
3(CH
2)
8CH
2O(C
2H
4O)
8SO
3H, CH
3(CH
2)
19CH
2O(C
2H
4O)
4SO
3H and CH
3(CH
2)
10CH
2O(C
2H
4O)
6SO
3H, sodium salts, potassium salts and amine salts of alkylnaphthylsulfonic acid.
[0045] Anionic surfactants commercially available and useful in the instant invention are
exemplified by dodecylbenzenesulfonic acid sold under the name Biosoft® S-100 by Stepan
Co. and related salts such as the sodium salt of dodecylbenzensulfonic acid sold under
the name Siponate
™ DS-10 by Alcolac Inc.
[0046] Nonionic surfactants useful in the method of our invention have a hydrophilic-lipophilic
balance (HLB) between 10 and 20. Nonionic surfactants with an HLB of less than 10
may be used in the instant invention, however, a hazy solution may result due to the
limited solubility of the nonionic surfactant in water. Preferably when using a nonionic
surfactant with an HLB of less than 10, a nonionic surfactant with an HLB of greater
than 10 should also be added during or after polymerization. The preferred nonionic
surfactants are those which are stable in the polymerization environment.
[0047] Examples of suitable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene
alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monoleates,
polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene
oxide-polypropylene oxide block copolymers, diethylene glycol, ethoxylated trimethylnonanols
and polyoxyalkylene glycol modified polysiloxane surfactants. Mixtures of nonionic
surfactants may also be employed.
[0048] Preferred nonionic surfactants are exemplified by 2,6,8 trimethyl-4-nonyloxypolyethyleneoxyethanol
(6EO) (sold as Tergitol® TMN-6 by Union Carbide Corp., Danbury, Conn. 06817), 2,6,8-trimethyl-
4-nonyloxypolyethylene-oxyethanol (10EO) (sold as Tergitol® TMN-10 by Union Carbide
Corp., Danbury, Conn. 06817), alkyleneoxypolyethyleneoxyethanol (C11-15, secondary
alkyl, 7EO) (sold as Tertitol® 15-S-7 by Union Carbide Corp., Danbury, Conn. 06817),
alkyleneoxypolyethyleneoxyethanol (C11-15, secondary alkyl, 9EO) (sold as Tergitol®
15-S-9 by Union Carbide Corp., Danbury, Conn. 06817), alkyleneoxypolyethyleneoxyethanol
(C11-15, secondary alkyl, 15EO) (sold as Tergitol® 15-S-15 by Union Carbide Corp.,
Danbury, Conn. 06817), octylphenoxypolyethoxyethanol (40EO) (sold as Triton® X405
by Robin and Haas Co., Philadelphia, PA.), nonylphenoxypolyethoxyethanol (10EO) (sold
as Makon™ 10 by Stepan Co.) and polyoxyethylene-23-lauryl ether (sold as Brij® 35L
by ICI Americas, Inc., Wilmington, Del. 19897).
[0049] Examples of suitable cationic surfactants include various fatty acid amines and amides
and their derivatives and the salts of the fatty acid amines and amides. Examples
of aliphatic fatty acid amines include dodecylamine acetate, octadecylamine acetate
and acetates of the amines of tallow fatty acids, homologues of aromatic amines having
fatty acids such as dodecylanalin, fatty amides derived from aliphatic diamines such
as undecylimidazoline, fatty amides derived from aliphatic diamines such as undecylimidazoline,
fatty amides derived from disubstituted amines such as oleylaminodiethylamine, derivatives
of ethylene diamine, quaternary ammonium compounds and their salts which are exemplified
by tallow trimethyl ammonium chloride, dioctadecyldimethyl ammonium chloride, didodecyldimethyl
ammonium chloride, dihexadecyl ammonium choride, alkyltrimethylammonium hydroxides
such as octyltrimethyl-ammonium hydroxide, dodecyltrimethylammonium hydroxide or hexadecyltrimethylammonium
hydroxide, dialkyldimethyl-ammonium hydroxides such as octyldimethylammonium hydroxide,
decyldimethylammonium hydroxide, didodecyl-dimethylammonium hydroxide, dioctadecyldimethylammonium
hydroxide, tallow trimethylammonium hydroxide, coconut oil, trimethylammonium hydroxide,
methylpolyoxyethylene cocoammonium chloride and dipalmityl hydroxyethylammonium methosulfate,
amide derivatives of amino alcohols such as beta-hydroxylethylstearylamide and amine
salts of long chain fatty acids.
[0050] The amount of surfactant(s) and water is not critical and may be readily determined
by one skilled in the art. Component (E'), the surfactant(s) and water, is present
in an amount of 0 to 1000 parts by weight, and preferably from 100 to 300 parts by
weight, per 100 parts by weight of components (A)-(D).
[0051] If the copolymers of this invention are produced by dispersion polymerization then
the mixture can further comprise (E''), at least one dispersant and water and the
dispersants are exemplified by water soluble organic polymers such as carboxymethyl
cellulose, gelatin, gum agar, polyvinyl alcohol, polyacrylic acid, polymeth-acrylic
acid, hydroxy propylmethyl cellulose, methyl cellulose, colloidal silica and colloidal
clay.
[0052] The amount of dispersant and water is not critical and may be readily determined
by one skilled in the art. Generally, component (E''), the dispersant(s) and water,
is present in an amount of 0 to 1000 parts by weight, and preferably from 100 to 300
parts by weight, per 100 parts by weight of components (A)-(D).
[0053] If the copolymers of this invention are produced by suspension polymerization then
the mixture can further comprise (E'''), at least one suspending agent and water and
the suspending agents are exemplified by water insoluble inorganic dispersants such
as hydroxyapatite, barium sulfate, kaolin and magnesium silicates.
[0054] The amount of suspending agent(s) and water is not critical and may be readily determined
by one skilled in the art. Generally, component (E'''), the suspending agent(s) and
water, is present in an amount of 0 to 1000 parts by weight, and preferably from 100
to 300 parts by weight, per 100 parts by weight of components (A)-(D).
[0055] The method of our invention can further comprise adding a base compound to the product
of step (I) when component (A) is a vinyl ester. The base compound is exemplified
by sodium hydroxide, potassium hydroxide and ammonium hydroxide.
[0056] The temperature at which the mixture of components (A)-(D) and optionally (E) is
heated is dependent on the type of catalyst that is selected. However, it is preferred
for purposes of this invention that the mixture of components (A)-(D) and optionally
(E) is heated at a temperature of at least 50°C. and preferably from 50°C. to 100°C.
[0057] The general principles of free radical polymerization methods are well understood
by those skilled in the art. The desired monomer(s) and macromonomers are all placed
in a reactor with a sufficient amount of a mutual solvent so that when the reaction
is complete the viscosity of the reaction is reasonable. Undesired terminators or
inhibitors, such as oxygen, can be removed as needed by evacuation or by purging with
an inert gas, such as argon or nitrogen. The initiator is introduced and the reaction
brought to the temperature needed for initiation to occur, assuming thermal initiators
are used. The polymerization is allowed to proceed as long as needed for a high level
of conversion to be achieved, typically from a few hours to a few days. The solvent
is then removed, usually by evaporation or by precipitating the copolymer by addition
of a non-solvent. The copolymer can be further purified, as needed utilizing a variety
of techniques including filtration, extraction, trituration, membrane separation and
gel permeation chromatography.
[0058] There are numerous variations on these procedures, for example, the choice of degassing
method and gas, choice of initiator type, extent of conversion, reaction loading etc.
The choice of initiator and solvent are often determined by the requirements of the
particular monomers and macromonomers used, because different monomers and macromonomers
have different solubilities and different reactivities with a specific initiator.
[0059] The graft copolymers of this invention can also be prepared by first preparing the
backbone and polydiorganosiloxane side chains from the copolymerization of suitable
ethylenically unsaturated monomers and acryloxyalkyl - functional polydiorganosiloxane
macromonomers, followed by further polymerization of the resulting intermediary copolymer
with suitable polybutylene macromonomers to form the side chains. In yet another alternative
method, the polydiorganosiloxane side chain can be added by polymerizing siloxane-containing
moieties onto an intermediate copolymer prepared from suitable monomers and a polybutylene
macromonomer.
[0060] Analysis of the copolymer reaction product, the extracted materials and the purified
graft copolymer can be performed by conventional analysis techniques known in the
art. These include nuclear magnetic resonance (NMR), infrared molecular spectroscopies,
gel permeation/size exclusion chromatography, membrane osmometry, atomic absorption
and emission spectroscopies.
[0061] The carboxyl-functionality on the polybutylene macromonomer is useful when copolymerized
with polydiorganosiloxane macromonomer and other organic monomers and also serves
as a site for crosslinking. The polybutylene functions to reduce the water vapor permeability
of the copolymer. Typical crosslinkers include melamine resins, isocyanates, zinc
oxide, diamines and organofunctional silanes such as N-(beta-aminoethyl)-gamma-aminopropyltrimethoxysilane.
[0062] The carboxyl-functional group on the polybutylene macromonomer can also be neutralized
with base to render the copolymer water or alcohol soluble or dispersible. The graft
copolymer can also act as a dispersing agent or polymeric surfactant.
[0063] The carboxyl-functionality on the polybutylene macromonomer can also aid adhesion
to metal, wood and paper substrates.
Example 1 - Synthesis of Methacryloxy Endcapped Polydimethylsiloxane Macromonomer
[0064] Anionic polymerizations were conducted in rigorously cleaned and dried 3-necked round-bottom
flasks equipped with a stirrer and condenser under purified nitrogen atmosphere. A
2025 g xylene solution of a cyclic siloxane (1350 g) having the formula ((CH
3)
2SiO
2/2)
3, was added into the flask with a syringe. A calculated amount (76 mL) of 1.6 M n-butyl
lithium was added to initiate the ring-opening polymerization. 135 g of DMF (dimethyl
formamide) was added next. The reaction was allowed to proceed for 2 hours at 24°C.
The polymerization was allowed to proceed for 2 hours at 24°C. The polymerization
was terminated by the addition of 30 g of 3-(methacryloxypropyl)dimethylchlorosilane
(MAPDCS) to afford the macromonomer. The solution was filtered and devolatilized to
produce a macromonomer with a number average molecular weight (Mn) of 10,000 (denoted
hereinafter as Polydimethylsiloxane Macromonomer A).
[0065] A second methacryloxy endcapped poly(dimethylsiloxane) macromonomer was prepared
according to the procedure outlined above and this produced a macromonomer having
an Mn of 5,000 (denoted hereinafter as Polydimethylsiloxane Macromonomer B).
Example 2 - Synthesis of Acryloxy Endcapped Polyisobutylene Macromonomer
[0066] A polyisobutylene macromonomer was prepared according to Example 1 of U.S. Patent
5,665,828. The polyisobutylene macromonomer is a mixture of (i) a compound having
the formula:
and (ii) a compound having the formula
wherein Z denotes a polyisobutylene chain, wherein the polyisobutylene macromonomer
has a number average molecular weight of 1,100 (denoted hereinafter as Polybutylene
Macromonomer).
Example 3 - Synthesis of poly(methyl acrylate)-graft-polydimethylsiloxane
[0067] To a solution of 240.31 g of methyl acrylate and 60.07 g of Polydimethylsiloxane
Macromonomer A in 910 g of toluene was added 1.53 g of AIBN initiator. The resulting
solution was heated at 60°C. for 21 hours. The solution was poured into methanol to
precipitate the copolymer. The copolymer was dried under reduced pressure at 80°C.
for 20 hours to yield 270.1 g. The resulting copolymer contained the following weight
percentages of monomers and macromonomers: 80 wt% methyl acrylate/20 wt% Polydimethylsiloxane
Macromonomer A.
Example 4 - Synthesis of poly(methyl acrylate)-graft- (polybutylene-polydimethylsiloxane)
[0068] To a solution containing 33.40 g of methyl acrylate, 13.39 g of Polydimethylsiloxane
Macromonomer A and 20.08 g of Polyisobutylene Macromonomer in 261 g of toluene was
added 0.33 g of AIBN initiator. The resulting solution was heated at 60°C. for 20
hours. The solution was poured into methanol to precipitate the copolymer. The copolymer
was dried under reduced pressure at 80°C. for 16 hours to yield 56.60 g. The resulting
copolymer contained the following weight percentages of monomers and macromonomers:
50 wt% methyl acrylate/30 wt% Polyisobutylene Macromonomer/20 wt% Polydimethylsiloxane
Macromonomer A.
Example 5 - Synthesis of poly(methyl acrylate)-graft-(polybutylene-polydimethylsiloxane)
[0069] To a solution of 5.10 g of methyl acrylate, 10.02 g of Polydimethylsiloxane Macromonomer
A and 35.11 g of Polyisobutylene Macromonomer in 266 g of toluene was added 0.26 g
of AIBN initiator. The resulting solution was heated at 60°C. for 22 hours. The solution
was poured into methanol to precipitate the copolymer. The copolymer was dried under
reduced pressure at 80°C. for 16 hours to yield 44.64 g. The resulting copolymer contained
the following weight percentages of monomers and macromonomers: 10 wt% methyl acrylate/70
wt% Polyisobutylene Macromonomer/20 wt% Polydimethylsiloxane Macromonomer A.
Example 6 - Synthesis of poly(methyl acrylate)-graft-(polybutylene-polydimethylsiloxane)
[0070] To a solution of 50.01 g of methyl acrylate, 20.06 g of Polydimethylsiloxane Macromonomer
B and 30.11 g of Polyisobutylene Macromonomer in 409 g of toluene was added 0.51 g
of AIBN initiator. The resulting solution was heated at 60°C. for 21 hours. The solution
was poured into methanol to precipitate the copolymer. The copolymer was dried under
reduced pressure at 80°C. for 16 hours to yield 71.24 g. The resulting copolymer contained
the following weight percentages of monomers and macromonomers: 50 wt% methyl acrylate/30
wt% Polyisobutylene Macromonomer/20 wt% Polydimethylsiloxane Macromonomer B.
Example 7 - Synthesis of poly(methyl acrylate)-graft-(polybutylene-polydimethylsiloxane)
[0071] To a solution of 5.03 g of methyl acrylate, 10.03 g of Polydimethylsiloxane Macromonomer
B and 35.12 g of Polyisobutylene Macromonomer in 279 g of toluene was added 0.25 g
of AIBN initiator. The resulting solution was heated at 60°C. for 18 hours. The solution
was poured into methanol to precipitate the copolymer. The copolymer was dried under
reduced pressure at 80°C. for 16 hours to yield 43.16 g. The resulting copolymer contained
the following weight percentages of monomers and macromonomers: 10 wt% methyl acrylate/70
wt% Polyisobutylene Macromonomer/20 wt% Polydimethylsiloxane Macromonomer B.
Table 1
Copolymer Compositions |
Monomer |
EXAMPLE 4 |
EXAMPLE 5 |
EXAMPLE 6 |
EXAMPLE 7 |
EXAMPLE 3 |
PDMS Macromonomer A (MW= 10000) |
20 |
20 |
----- |
----- |
20 |
PDMS Macromonomer B (MW=5000) |
----- |
----- |
20 |
20 |
----- |
Methyl Acrylate |
50 |
10 |
50 |
10 |
80 |
PIB Macromonomer (MW=1100) |
30 |
70 |
30 |
70 |
----- |
*- PDMS denotes Polydimethylsiloxane |
*- PIB denotes Polyisobutylene |
Water Vapor Permeation
[0072] Water vapor permeation was measured on a Mocon Permtran-W 3/31 Water Vapor Permeation
Analysis System. The films of Examples 3, 4 and 6 were tested at 85-90% relative humidity.
Film thicknesses were all between 0.3 and 0.35 mm. The water vapor permeation rates
given are equilibrium values. The results are shown in Table 2.
Table 2
Example |
Thickness (mm) |
Wt% PIB Macromonomer |
MW of PDMS Macromonomer |
Water Vapor Permeation (g/m2/day) |
3 |
0.30 |
0 |
10,000 |
108 |
4 |
0.34 |
30 |
10,000 |
35 |
6 |
0.30 |
30 |
5,000 |
41 |
Water Repellency
[0074] The dimensional stability of films cast from the terpolymers of this invention were
visibly better than the methyl acrylate-graft-silicone copolymer control or the poly(methyl
acrylate) control. After submerging the films in water for 172 hours, the polyisobutylene
- containing polymer films were perfectly flat, whereas the other films were curled
and wrinkled.
1. A graft copolymer comprising a backbone and at least two polymeric side chains, the
graft copolymer formed from the copolymerization of randomly repeating ethylenically
unsaturated monomer units, acryloxyalkyl-functional polydiorganosiloxane macromonomer
units and acryl-terminated, carboxyl-functional polybutylene macromonomer units, wherein
the copolymer comprises:
(A) at least one ethylenically unsaturated monomer selected from acrylic acid esters,
vinyl esters, N-alkyl acrylamides, alkyl vinyl ethers, alkyl substituted styrenes
or acrylonitrile;
(B) at least one acryl-terminated, carboxyl-functional polybutylene macromonomer having
its formula selected from
(i)
(ii)
(iii) a mixture of (i) and (ii),
(iv)
(v)
(vi) a mixture of (iv) and (v),
(vii)
(viii)
(ix)
(x) a mixture of (viii) and (ix),
(xi)
(xii)
(xiii) a mixture of (xi) and (xii),
(xiv)
(xv)
(xvi) a mixture of (xiv) and (xv),
(xvii)
(xviii)
and
(xix) a mixture of (xvii) and (xviii) wherein Z represents a polybutylene chain, G
is independently an alkylene group having 2 to 10 carbon atoms, G' is independently
an alkylene group having from 1 to 10 carbon atoms, L is independently selected from
hydrogen or an alkyl group having from 1 to 18 carbon atoms, R2 is selected from methyl, ethyl or propyl and R1 is independently an alkyl radical having from 1 to 6 carbon atoms; and
(C) at least one acryloxyalkyl-functional polydiorganosiloxane macromonomer, wherein
the ethylenically unsaturated monomer units, in conjunction with the copolymerizable
moieties of the acryloxyalkyl-functional polydiorganosiloxane macromonomer units and
the acryl-terminated, carboxyl-functional polybutylene macromonomer units, form the
backbone, and wherein the polymeric portion of the acryloxyalkyl-functional polydiorganosiloxane
macromonomer units form at least one side chain and the polymeric portion of the acryl-terminated,
carboxyl-functional polybutylene macromonomer units form at least one side chain.
2. A graft copolymer according to Claim 1, wherein (C) is an acryloxyalkyl-functional
organopoly-siloxane having the formula:
wherein R
6 is an alkyl group having from 1 to 18 carbon atoms, R
7 is an alkyl group having from 1 to 10 carbon atoms, a has a value of at least 1,
preferably at least 3, and more preferably at least 10, and Y is a group having the
formula -R
9-O-C(O)-CR
8=CH
2, wherein R
8 is selected from hydrogen or an alkyl group having from 1 to 18 carbon atoms and
R
9 is an alkylene group having from 1 to 10 carbon atoms.
3. A graft copolymer according to claim 2 wherein R6 is methyl, R7 is selected from methyl, ethyl, propyl, n-butyl, sec-butyl or tert-butyl, R8 is hydrogen or methyl, R9 is selected from ethylene, propylene or butylene and a has a value of from 10 to
300.
4. A method of making graft copolymers comprising randomly repeating ethylenically unsaturated
monomer units, acryl-terminated, carboxyl-functional polybutylene units and acryloxyalkyl-functional
polydimethylsiloxane units, the method comprising (I) heating a mixture comprising:
(A) at least one ethylenically unsaturated monomer selected from acrylic acid esters,
vinyl esters, N-alkyl acrylamides, alkyl vinyl ethers, alkyl substituted styrenes
or acrylonitrile;
(B) an acryl-terminated, carboxyl-functional polybutylene macromonomer having a formula
selected from
(i)
(ii)
(iii) a mixture of (i) and (ii),
(iv)
(v)
(vi) a mixture of (iv) and (v),
(vii)
(viii)
(ix)
(x) a mixture of (viii) and (ix),
(xi)
(xii)
(xiii) a mixture of (xi) and (xii),
(xiv)
(xv)
(xvi) a mixture of (xiv) and (xv),
(xvii)
(xviii)
or
(xix) a mixture of (xvii) and (xviii) wherein Z represents a polybutylene chain, G
is independently an alkylene group having 2 to 10 carbon atoms, G' is independently
an alkylene group having from 1 to 10 carbon atoms, L is independently selected from
hydrogen or an alkyl group having from 1 to 18 carbon atoms, R2 is selected from methyl, ethyl or propyl and R1 is independently an alkyl radical having from 1 to 6 carbon atoms, (C) an acryloxyalkyl-functional
polydiorganosiloxane macromonomer and (D) an initiator.
5. A method according to claim 4 wherein (C) is an acryloxyalkyl-functional organopolysiloxane
having the formula:
wherein R
6 is an alkyl group having from 1 to 18 carbon atoms, R
7 is an alkyl group having from 1 to 10 carbon atoms, a has a value of at least 1,
preferably at least 3, and more preferably at least 10, and Y is a group having the
formula -R
9-O-C(O)-CR
8=CH
2 , wherein R
8 is selected from hydrogen or an alkyl group having from 1 to 18 carbon atoms and
R
9 is an alkylene group having from 1 to 10 carbon atoms.
6. A method according to claim 5 wherein R6 is methyl, R7 is selected from methyl, ethyl, propyl, n-butyl, sec-butyl or tert-butyl, R8 is hydrogen or methyl, R9 is selected from ethylene, propylene or butylene and a has a value of from 10 to
300.
7. A method according to claims 4 , 5 or 6 wherein (D) is selected from dibenzoyl peroxide,
t-butyl peroctoate, dicumyl peroxide, diisopropyl peroxydi-carbonate or 2,2-azobisisobutyronitrile.
8. A method according to claim 4 wherein the mixture further comprises (E) a solvent.
9. A method according to claim 4 wherein the mixture further comprises (E') at least
one surfactant selected from (i) at least one anionic surfactant, (ii) at least one
nonionic surfactant, (iii) at least one cationic surfactant, a mixture of (i) and
(ii) or a mixture of (ii) and (iii) and water.
10. A method according to Claim 4, wherein the mixture further comprises (E'') at least
one water soluble organic polymer dispersant selected from carboxymethyl cellulose,
gelatin, gum agar, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, hydroxy
propylmethyl cellulose, methyl cellulose, colloidal silica or colloidal clay and water.
11. A method according to claim 4 wherein the mixture further comprises (E''') at least
one suspending agent and water, wherein the suspending agents are water insoluble
inorganic dispersants selected from hydroxyapatite, barium sulfate, kaolin or magnesium
silicates..
12. A method according to claim 4 wherein the mixture of (I) is heated at a temperature
of from 50°C. to 100°C.
13. A method according to claim 4 wherein the method further comprises adding a base compound
to the product of step (I).